Darstellung und Kristallstruktur von Lithiumhydrogensulfid,LiHS

Preparation and Crystal Structure of Lithiumhydrogensulfide, LiHS Lithiumhydrogensulfide, LiHS, is prepared from lithiumamide, LiNH₂, by reaction with liquid hydrogensulfide. At 150°C the solubility of LiHS in H₂S is sufficient for the growth of single crystals in a temperature gradient within the autoclaves used. The X-ray structure determination at 295 K is characterized by the following data: Lithium occupies tetrahedral sites in a distorted cubic close-packed arrangement of S; in PtS sulfur occupies tetrahedral sites in a similar way in a distorted close packing of Pt. Hydrogen atoms of the HS^??ions are dynamically disordered in a split position linearly bound to S. At 228 K a thermal effect occurs in DSC-measurements indicating that below this temperature the HS^??ion has fixed positions.     

Kristallstruktur und elektrische Leitfähigkeit von Li2–2xMn1+xCl4-Spinelltyp-Mischkristallen

Crystal Structure and Electric Conductivity of Spinel-Type Li_2–2xMn_1+xCl₄ Solid Solutions The electric conductivity of the fast lithium ion conductors Li_2–2xMn_1+xCl₄ was measured by impedance spectroscopic methods. The conductivities obtained, e.g. ～ 4 × 10^?1 Ω^?2 cm^?1 at 570 K, depend only little on the lithium content. The crystal structure of Li_1.6Mn_1.2Cl₄ was determined by neutron powder and X-ray single crystal diffraction (space group Fd3 m, Z = 8, a = 1 049.39(6) pm, R_w = 1.4% on the basis of 170 reflections). The lithium deficient chloride crystallizes in an inverse spinel structure like the stoichiometric compound Li₂MnCl₄ according to the formula (Li_0,8)[Li_0,4Mn_0,6]₂Cl₄ with vacancies ( ) at the tetrahedral sites. The decrease of the M_oct? Cl distances with the increase of x reveals that the ionic radius of Mn²⁺ in chlorides is equal or even smaller than that of Li⁺ opposite to fluorides and oxides. The ? Cl distances of spinel type chlorides are 237 ( _tet) and 274 pm ( _oct), respectively. The mechanism of the ionic conductivity is discussed.     

Über Chalkogenolate. 101. Untersuchungen über Halbester der Monothiokohlensäure. 1. Darstellung und Eigenschaften von Oxoxanthaten

On Chalcogenolates. 101. Studies on Hemiesters of Monothiocarbonic Acid. 1. Preparation and Properties of Oxoxanthates Alkyl oxoxanthates of alkali metals have been prepared by reaction of COS with the corresponding alkoxides. The reaction of ethyl oxoxanthate with methyl iodide leads to S-methyl-O-ethyl ester of monothiocarbonic acid. The oxidation of [SOC? OC₂H₅]^? ions with iodine forms bis(ethoxycarbonyl)-disulfide (S? CO? OC₂H₅)₂. The prepared compounds have been characterized with chemical and thermoanalytical methods as well as by means of electron absorption spectra, infrared spectra, ¹H-NMR spectra, and mass spectra.     

Ungewöhnliche H-Brückenbindungen in Natriumhydroxidmonohydrat: Röntgen- und Neutronenbeugung an NaOH · H2O bzw. NaOD · D2O

Unusual H-Bonds in Sodium Hydroxide Monohydrate: X-Ray and Neutron Diffraction on NaOH · H₂O and NaOD · D₂O, respectively X-ray data revealed the structure of NaOH · H₂O including the H positions. Neutron diffraction on microcrystalline NaOD · D₂O was used for comparison of H with D positions: The compound crystallizes in a layer-type structure with the sequence …? /O Na O O Na O/ …? closely related to that of hydrargillite Al(OH)₃ with …? /O 2/3 Al O O 2/3 Al O/ …?. Between OH^? ions as acceptors and H₂O molecules mäandric, one-dimensional infinite strong H-bonds occur with d(O…?O) = 2.66 Å and 2.69 Å. These lie within O-layers that coordinate Na⁺ ions. Bridge-bonds between OH^? ions as donors and H₂O molecules as acceptors connect the /O Na O/-layers with d(O…?O) = 3.18 Å.     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide. XXX [1]. Nickel-, Palladium- und Platinkomplexe primärer Mercaptoalkylphosphine

Primäre Mercaptoalkylphosphine H₂ (H₂P? CH₂? CH₂? SH; H₂P? CH₂? CHCH₃? SH) reagieren mit Salzen der d⁸-Metalle zu planaren 1:2-Chelatkomplexen. Synthese, Struktur und Eigenschaften der Koordinationsverbindungen werden diskutiert, wobei besonderes Interesse der Alkylierbarkeit des Schwefels sowie dem reaktiven Verhalten des primären Phosphinphosphors gilt. Letzterer läßt sich mit Kalium metallieren und anschließend mit geeigneten Alkylhalogeniden in Derivate mit sekundärem Phosphinphosphor überführen. On the Coordination Chemistry of Phosphines and Phosphinoxides. XXX. Nickel, Palladium, and Platinum Complexes of Primary Mercaptoalkylphosphines Primary Mercaptoalkylphosphines H₂ (H₂P? CH₂? CH₂? SH; H₂P? CH₂? CHCH₃? SH) react with d⁸-metal salts to give planar 1:2 chelat complexes. Synthesis, structure, and properties of these compounds are discussed. Special interest apply to the alkylation of sulphur and the reactive behaviour of the primary phosphine phosphorus. The latter can be metalled by potassium and after that it is possible to alkylate with suitable alkyl halides to give derivates with secondary phosphine phosphorus.     

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit verschiedenen 1H-Phosphiren-Liganden,Kristallstrukturen von,und

Synthesis and Spectroscopic Characterization of some Pentacarbonyltungsten(0) Complexes with Various 1H-Phosphirene Ligands: Crystal Structures of , and The tungsten(0) complex 1 reacts upon heating with acetylene derivatives 2a–f in toluene to form benzonitrile and the complexes 4a–f ( 4a : R¹ ? Ph, R² ? H; 4b : R¹ ? Ph, R² ? CH₃; 4c : R¹ ? OEt, R² ? H; 4d : R¹ ? Ph, R² ? CO₂Et; 4e : R¹, R² ? CO₂Me; 4f : R¹, R² ? SiMe₃), which have been isolated by chromatography. Spectroscopic and mass spectrometric data are discussed. The crystal structures of the compounds 4a, b and d were determined by X-ray single crystal structure analysis ( 4a : space group P2₁/n, Z = 4, a = 937,5(2) pm, b = 2202,4(6) pm, c = 1266,3(4) pm, β = 108,94(4)°; 4b : space group P2₁/c, Z = 4, a = 1293,9(2) pm, b = 923,5(1) pm, c = 2223,4(3) pm, β = 92,385(6)°; 4d : space group P2₁/c, Z = 4, a = 955,2(2) pm, b = 3190,9(4) pm, c = 930,7(2) pm, β = 99,64(1)°).     

Beiträge zur Chemie der Halogensilan-Addukte. XXII. Wasserstoffbrückenbindung und Ionisierung Pentakoordinierter SiCl-Verbindungen. Darstellung,Eigenschaften, Kristall- und Molekülstruktur von 2,2-Dimethyl-2,3-dihydro-1H-[1,4,2]diazasilolo[4,5-α]pyridiniumchlorid-Chloroform(1/1),

Contributions to the Chemistry of Halosilane Adducts. XXII. Hydrogen Bonding and Ionization of Pentacoordinated Si-Compounds. Preparation, Properties, Crystal and Molecular Structure of 2,2-Dimethyl-2,3-dihydro-1H-[1,4,2]diazasilolo[4,5-α]pyridinium-chloride-Chloroform(1/1), The title compound ( 1 ) is obtained by the reaction of 2-trimethylsilylaminopyridine and Me₂CH₂ClSiCl in CHCl₃. The SiCl bond is ionic (X-ray structure determination). 1 crystallizes monoclinic space group P2₁/c (Z = 8). The asymmetric unit contains two symmetrically nonequivalent molecular cations of 1 , two Cl anions and two CHCl₃. Silicon is tetracoordinate with Si? N-bond distances of 1.766 Å and 1.777 Å. The shortest SiCl distances (3.908 and 4.110 Å) correspond to ionic interactions. Both Cl anions are hydrogen bonded to CHC1₃. Additionally one C1_? is hydrogen bonded to the NH groups of two neighbouring cations. Structural comparison with related compounds suggests these interactions to be responsible for the transition from pentacoordination to tetracoordination at Si (ionization of the Sic1 bond). ¹H- and ²⁹Si-NMR investigations of 1 show this transition to be dependent on the combined effect of NH…?C1^? and C1₃CH…?C1_? interactions. 1 is completely ionized in CDCl₃ in the temperature range ?80° to +80°C while in the weaker acceptor solvent benzonitrile a temperature dependent shift from the ionic tetracoordinate to the pentacoordinate structure is observed with increasing pentacoordination with increase of temperature.     

Kinetic study of the iodine-catalyzed alcoholysis of Butoxytriethylsilane: n-butoxy group—s-butoxy group exchange reaction

In order to appreciate the excellent catalytic effect of iodine on the alcoholyses of alkoxysilanes more precisely, the rates of the reaction, Et₃SiOBuⁿ + Bu^sOH ? Et₃SiOBu^s + BuⁿOH, were determined at various iodine concentrations. Both forward and reverse reactions are first order with respect to butoxysilane and to butanol, and pseudo first-order rate constants were measured at 40°, 30°, and 20°C on reaction mixtures containing both butanols in excess by means of gas-liquid chromatography. The observed rate constants as a function of iodine concentration gave linear relationships, and from these data the catalytic coefficients of iodine were evaluated: The enthalpies and the entropies of activation were estimated to be 53.2 kJ mol^?1, ?103 J K^?1 mol^?1 (forward, 30°C) and 51.8 kJ mol^?1, minus;100 J K^?1 mol^?1 (reverse, 30°C).     

Synthese und Kristallstruktur von Alkalimetalldiamidodioxosilicaten M2SiO2(NH2)2 mit M ≙ K,Rb und Cs

Synthesis and Crystal Structure of Alkali Metal Diamido Dioxosilicates M₂SiO₂(NH₂)₂ with M ? K, Rb and Cs SiO₂ – α-quartz – reacts with alkali metal amides MNH₂ (M ? K, Rb, and Cs) in molar ratios from 1:2 to 1:10 at 450°C ≤ T ≤ 600°C and P(NH₃) = 6 kbar in autoclaves to diamidodioxosilicates M[SiO₂(NH₂)₂]. Crystals of the colourless compounds which hydrolyze rapidly were investigated by x-ray methods. Following data characterize the structure determination on the isotypic compounds: The structures of the diamidodioxosilicates are closely related to the β? K₂SO₄ type. They contain isolated [SiO₂(NH₂)₂]^2? ions. K⁺ ions and hydrogen bridge bonds N? H…?O (with 2.68 Å ≤ d(N…?O) ≤ 2.78 Å for the K compound) connect the tetrahedral anions.     

AlCl3 · 3NH3 — eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-diammintetrachloroaluminats: [AlCl2(NH3)4]+[AlCl4(NH3)2]−

AlCl₃ · 3NH₃ — a Compound with the Crystal Structure of a Tetraammine Dichloro Aluminium-Diammine Tetrachloro Aluminate: [AlCl₂(NH₃)₄]⁺[AlCl₄(NH₃)₂]^? . AlCl₃ · 3 NH₃ ? [AlCl₂(NH₃)₄]⁺ [AlCl₄(NH₃)₂]^? forms during the reaction of two mole NH₃ with AlCl₃(NH₃) at T ≥ 200°C. Repeated heating and cooling within 48 h between 200°C and 250°C gives a homogeneous product with total uptake of the necessary amount of NH₃. Slow sublimation in a vacuum line apparatus at 200°C gives crystals of the triammoniate sufficient for a X-ray structure determination: The compound contains elongated [AlCl₂(NH₃)₄]⁺ octahedra and compressed [AlCl₄(NH₃)₂]^? octahedra. Besides ionic bonding hydrogen bridge bonds with 3.369 Å ? d(N—H … Cl) ? 3.589 Å stabilize the atomic arrangement.     

Silaethene. III. Versuche zur Darstellung und spektroskopischen Charakterisierung von H2SiCH2, D2SiCH2 und Me(H)SiCH2

Silaethenes. III. Preparation and Spectroscopic Characterization of H₂Si?CH₂, D₂Si?CH₂, and Me(H)Si?CH₂ H₂Si?CH₂ and D₂Si?CH₂ are formed together with ethene and propene by gas phase pyrolysis at low pressure (10^?2–10^?3 mbar) from the corresponding mono- or 1,3-disilacyclobutanes in good yield and are characterized by i.r. and mass spectroscopic methods. Formation of propene can be explained by following reactions of the silaethene intermediate using a “head-to-head” mechanism. H₂Si?CH₂ can be stored at ?196°C for several months and can be transferred by trap-to-trap distillation in a vacuum system. Similar results are obtained for .     

Diphenylacetylen-Komplexe von Niob,Molybdän,Wolfram und Rhenium Die Kristallstruktur von [NbCl3(Ph?CC?Ph)]4

Diphenylacetylene Complexes of Niobium, Molybdenum, Tungsten, and Rhenium. Crystal Structure of [NbCl₃(Ph? C?C? Ph)]₄ Syntheses and i.r. spectra of the following diphenylacetylene complexes are reported: The chloro complexes 1, 2, 4, 7 and 8 are formed in the pentachlorides of niobium, molybdenum, rhenium, and tungsten hexachloride, respectively, with diphenyl acetylene. The bromo and iodo complexes 3, 5 and 6 are obtained by halogen exchange with boron halides, and the derivatives 9, 10 and 11 are obtained by reactions of PPh₄Cl or AsPh₄Cl and PPh₃ with the corresponding starting materials. The crystal structure of 1 was determined by the aid of X-ray diffraction data (R = 5.9% for 1548 independent, observed reflexions). The complex crystallizes triclinic in the space group P1 with one tetrameric molecule [NbCl₃(Ph? C?C? Ph)]₄ per unit cell. The cell dimensions at 20°C are a = 1074 pm, b = 1390 pm, c = 1299 pm, α = 104.3°, β = 108.0°, γ = 108.7°. 1 occurs as a centrosymmetric tetramer, which can be regarded as a distorted double hexahedron with two corners missing. Association is effected by chloro bridges in which the chlorine atoms have coordination number two and three. The diphenylacetylene ligands are bonded to the niobium atoms side-on with almost equal Nb? C bond lengths of average value 205 pm. Thus the Nb atoms achieve coordination number seven.     

Die Kristallstruktur von K2S3 und K2Se3

The Crystal Structure of K₂S₃ and K₂Se₃ Well formed crystals of K₂S₃ and K₂Se₃ were obtained by reaction of the elements in liquid ammonia at 500 bar and 150°C. The substances are both orthorhombic, space group Cmc2₁. Cell constants are: The structure contains S₃^2?(Se₃^2?) polyanions, with S? S? S(Se? Se? Se) angles of 105.4(102.5)°. The S? S(Se? Se) distance is 2.083(2.383) Å.     

The carbon–hydrogen bond strength in dimethyl ether and some properties of iodomethyl methyl ether

The kinetics and mechanism of the reaction between iodine and dimethyl ether (DME) have been studied spectrophotometrically from 515–630°K over the pressure ranges, I₂ 3.8–18.9 torr and DME 39.6–592 torr in a static system. The rate-determining step is, where k₁ is given by log (k₁/M^?1 sec^?1) = 11.5 ± 0.3 – 23.2 ± 0.7/θ, with θ = 2.303RT in kcal/mole. The ratio k₂/k_?1, is given by log (k₂/k_?1) = ?0.05 ± 0.19 + (0.9 ± 0.45)/θ, whence the carbon-hydrogen bond dissociation energy, DH° (H? CH₂OCH₃) = 93.3 ± 1 kcal/mole. From this, ΔH°_f(CH₂OCH₃) = ?2.8 kcal and DH°(CH₃? OCH₂) = 9.1 kcal/mole. Some nmr and uv spectral features of iodomethyl ether are reported.     

Ein ungewöhnliches H-Brückenbindungssystem in Rubidium-hydroxiddihydrat,RbOH · 2 H2O

An Unusual System of Hydrogen Bonds in Rubidium Hydroxide Dihydrate, RbOH · 2 H₂O RbOH · 2H₂O was obtained by the reaction of Rb with H₂O and dehydration of the resulting solution by concentrated sulfuric acid. The compound melts at 310 K. The structure was determined by X-ray single crystal methods: The H positions of H₂O were found. The structure consists of a threedimensional H-bonded network of H₂O molecules and OH^?ions. Hydroxide ions are acceptors for four protons of four adjacent water molecules with d(O? O) = 2×2.59 Å and 2×2.82 Å. Oxygen of OH-ions is disordered over a distance of 1.27 Å. Rb has 8 H₂O molecules as nearest neighbours, d(Rb? O) = 3.03 Å to 3.07 Å, OH^?ions are further removed with d(Rb? O) ≥ 3.45 Å.     

Chemie polyfunktioneller Moleküle. 118 [1]. Synthesen und Kristallstrukturanalysen von bicyclischen Metallaphosphazenen des Platins und Eisens mit vier- und sechsgliedrigen Ringen

Chemistry of Polyfunctional Molecules. 118. Syntheses and Crystal Structures of Bicyclic Metallaphosphazenes with Four and Six Membered Rings Anhydrous MCl₂ (M = Pt, Fe) react with LiN(PPh₂)₂ ( 1 ) in the molar ratio of 1:2 in boiling toluene within 25 hours under partially oxidative scrambling of the PNP chain in 1 yielding the bicyclic metallaphosphazenes 5 a, b . While compound 5 a can be isolated in substance, the intermediate 5 b proves to be highly reactive but can be stabilized in the presence of CO, forming the 18-valence-electron coordination compound as an isomeric trans( 6 a )/cis( 6 b ) mixture in the molar ratio of 99:1. Also treatment of anhydrous PtCl₄ with four equivalents of 1 in boiling toluene during 60 hours yields 5 a . Alkylation of 5 a with CH₃I leads to the formation of the ionic species [Pt²⁺{Ph₂P? N(CH₃)? PPh₂}(Ph₂P? N = PPh₂ = N? PPh₂^?)]I^? ( 9 ). The X-ray crystal structures of 5 a × 1 CH₂Cl₂ and 6 a reveal, that the metal centres have a planar P-coordination polyhedron in the solid state. In the complex 9 × 2,5 CH₂Cl₂ however the torsion angle between the P? Pt? P planes of the four and six membered rings shows to be 15°. The six membered metallacycles in 5 a × 1 CH₂Cl₂, 6 a and 9 × 2,5 CH₂Cl₂ differ in their geometrical arrangement. All the new compounds have also been characterized by their ¹H, ³¹P{¹H}, ¹³C{¹H} NMR, IR, Raman and mass spectra.     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide. XXXI. Cobalt- sowie Rhodiumkomplexe primärer Mercaptoalkylphosphine und Bemerkungen zur Komplexbildung quadridentater P,P,S,S-Liganden

On the Coordination Chemistry of Phosphines and Phosphinoxides. XXXI. Cobalt and Rhodium Complexes of Primary Mercaptoalkylphosphines and Remarks on the Complex Formation of Quadridentate P,P,S,S Ligands Primary Mercaptoalkylphosphines (H₂P? CH₂ · CH₂? SH; H₂P? CH₂ · CHCH₃? SH) react with d⁷-metal salts to give octahedron 1:3 chelat complexes. In case of cobalt the oxidation of Co^II to Co^III are obtained by formation of H₂. Structure and properties of these complexes as well as their reactivity like S-alkylation or metallation with following reactions are described. Reaction scheme see ?Inhaltsübersicht”?. With quadridentate ligands HS+ +PH+ +PH+ +SH = L result chelat-complexes of the type [M^III? L XNH₃] (M = Co, Rh) and such as [M^II? L] (M = Ni, Pd, Pt).     

Über Chalkogenolate. 92. Untersuchungen über Trithioallophansäure 1. Alkalimetalltrithioallophanate

On Chalcogenolates. 92. Studies on Trithioallophanic Acid 1. Trithioallophanates of Alkali Metals The trithioallophanates have been prepared by reaction of H₂S with the corresponding dithiocarbimate. The compounds have been characterized by different methods. In aqueous solution the equivalent conductivites of [S₂C? NH? CS? NH₂]^? have been determined by means of conductivity measurements. The Stokes radius of the ion, the radius of the hydrated ion, and its diffusion coefficient were calculated.     

Rubidium-Pentafluoromanganat(III) und dessen Monohydrat,strukturelle Daten und Topotaxiebeziehungen

Rubidiumpentafluoromanganate (III) and its monohydrate, crystal data and topotaxy The unit cells and most probable space groups of the new compounds Rb₂MnF₅ · H₂O and Rb₂MnF₅ have been determined from single crystal X-ray diffraction data and the powder diffraction patterns indexed. . By analogy to the stoichiometrically similar phases high temperature K₂MnF₅ · H₂O, the unit cell of which has also been determined and its powder diffraction pattern indexed, and (NH₄)₂MnF₅, model structures for the rubidium salts are proposed. Both structures consist of infinite chains of corner sharing coordination octahedra [MnF₆], between which the rubidium ions and in the case of the hydrate additional water molecules are located. X-ray diffraction and scanning electron microscopical investigations of the dehydration of the hydrate clearly point to a chain controlled topotactic reaction mechnism. This supports the proposed model structures and confirms the possibility of predicting topotactic reaction mechanisms.     

Cycloadditionsreaktionen von Trifluormethylisocyanid an Diphosphene. Synthese und Struktur des neuartigen 2-Phosphiniden-1, 3-azaphospholidins

Cycloaddition Reactions of Trifluoromethyl Isocyanide with Diphosphenes. Synthesis and Structure of the new 2-Phosphinidene-1,3-azaphospholidine Derivative [2 + 1] Cycloaddition reactions of trifluoromethyl isocyanide 1 and methylisocyanide 2 with the diphosphene R? P?P? R 3a ( a R ? C[Si(CH₃)₃]₃) yield the three membered heterocyclic diphosphirane imines 4 and 5 , respectively. Whereas the trifluoromethyl substituted compound 4 is thermally very stable, the methylsubstitued derivative 5 slowly looses methyl isocyanide reforming the diphosphene 3a . In the reaction of 1 with R? P?P? R 3b [ b R = 2,4,6-(t-Bu)₃C₆H₂] no evidence for the formation of a three membered ring compound could be obtained. The five membered heterocycle 3-(2,4,6-Tri-t-butylphenyl)-2-[2,4,6-tri-t-butylphenyl)-phosphinidene]-1-trifluoromethyl-4, 5-bis(trifluoromethylimin)-1,3-azaphospholidine 6 was isolated as the only product together with unreacted 3b . The structure of 6 , triclinic, P1 , a = 1081.1(8), b = 1463.1(11), c = 1643.6(5)pm, α = 64.01(6), β = 81.22(4), γ = 74.04(5)°, Z = 2, R = 0.080, R_w = 0.085, has been elucidated by X-ray diffraction.